DE2451784A1 - Perylene 3,4,9, 10-tetracarboxylic acid diimide dyes - contg. ether gps., for use in paints, resins, printed inks, plastics etc. - Google Patents

Abstract

Perylene 3,4,9,10-tetracarboxylic acid diimide dyes of formula: (in which R is 1-8C alkyl, X is Cl or Br, n is 0-3, the R gps. may the the same or different) are used in paints, resins, printing inks and distempers, and for mass colouring of plastics, in bluish-red shades. Cpds. give strong shades with excellent light-fastness and good weather fastness. Dyes in which R is methyl or ethyl have very good to excellent fastness to solvents, over-painting and plasticisers. The other dyes are more soluble and are pref. for mass colouring of plastics. At higher processing temps. in thermoplastics, fluorescent orange shades are obtd.

Description

Perylene-3,4,9,10-tetracarboxylic acid diimide series dyes The invention relates to new dyes of the perylene-3,4,9,10-tetracarboxylic acid diimide series, their Manufacture and use for coloring lacquers, resins, printing inks, printing pastes and of plastics in bulk.

The new dyes, which are characterized by very good working properties, have the formula in which R is alkyl with 1 to 8 carbon atoms, X is carbon or bromine and n is a number between 0 and 3 and the radicals R can be identical or different, for R, alkyls are specifically: methyl, ethyl , n-propyl, iso-propyl, butyl, iso-butyl, 2-butyl, pentyl, hexyl, octyl, 2-ethylhexyl. Preferred alkyl radicals for R are lower alkyl radicals having 1 to 4 carbon atoms. Of the alkyl radicals mentioned, butyl, iso-butyl, 2 = butyl, n-propyl, iso ° propyl, in particular methyl or ethyl, are preferred for reasons of color and application technology.

The perylene radical can carry 1 to 3 chlorine or bromine atoms, preferably however, the remainder is unsubstituted; doho preferably n = 0.

The dyes can be obtained in a manner known per se by condensation of perylene-304,9,10-tetracarboxylic acid or their dianhydride with the corresponding aliphatic ether amines in solvents or diluents such as alcohols, e.g. isobutanol or 2-ethylhexanol, glycols, in a large excess the primary amines, which serve as solvents or, preferably, in water at higher temperatures such as 80 to 2000C, preferably 130 to 1800C, if necessary produce under pressure.

The dyes are isolated from the reaction mixture in a customary manner by filtration, if appropriate after diluting the reaction mixture with inert ones Solvents at normal temperature or also at temperatures between 40 and 10,000. The inert solvents are preferably water or alcohols such as Methanol or ethanol can be considered.

To remove any remaining traces of perylenetetracarboxylic acid you can use the dyes with a dilute, warm soda solution, sodium or potassium hydroxide solution treat. The dyes can, if desired, by reprecipitation from sulfuric acid or can be further purified by recrystallization.

The ether amines are used for reaction with perylenetetracarboxylic acid ZoBe in BetracbtO 2-pentoxyethylamine, 2-hexoxyethylamine, 2- (ß-Ätbylbexoxy) -ätbylamin, 2-n-propoxyethylamine, 2-n-butoxyethylamine, 2-methoxyethylamine and 2-Ätboyätbylamin.

Of the abovementioned Ätberaminen are economic and coloristic The reasons for this are 2-n-propoxyethylamine, 2-butoxyethylamine and, in particular, 2-methoxyethylamine and 2-ethoxyethylamine are particularly preferred.

The dyes are ideal for coloring paints, resins, Printing inks or printing pastes and for the mass coloring of synthetic plastics, especially of thermoplastic plastics such as polyvinyl chloride, polyethylene, Polypropylene, polystyrene and mixed polymers of styrene and polycarbonates. The dyes can also be run over in pigment preparations, which as they can be used for further staining. The new dyes can also as Vat dyes are used0 As pigment dyes can be used in the synthesis obtained seal dyes can be used directly in many cases. Advantageously If, however, the Rob dyes are to be used by means of Finisb measures, e.g. by transferring them in a finely divided form, such as by reprecipitation from sulfuric acid or by grinding, and subsequent recrystallization in water and / or organic solvents Convert into special finisbforms at a higher temperature in a manner known to slcb.

The dyes color paints and thermoplastic plastics, such as BO Polyvinyl chloride and polyethylene in a strong bluish shade of red with excellent Lightfastness and good weather resistance. The solvent, overcoating and weaving rights, as they are required for paint and white polyvinyl chloride dyeings are in particular in the case of the dyes in which R stands for methyl or ethyl, very good to excellent. In the full tones, very opaque blue-rustic red tones are obtained. in which R is an alkyl radical with more than 2 carbon atoms are in organic media More easily soluble and are particularly suitable for mass coloring plastics such as rigid PVC and polyethylene.

In plastics such as polystyrene and polycarbonate, the coarser processing temperatures than polyvinyl chloride and polyethylene require and at the coarse processing temperatures show a certain dissolving power for the dyes (I) are with the from the Syntbese obtained red to blue-red dye powders orange colorations In a transparent coloring, these fluoresce orange0 These colors also show A bobe lightfastnessO Naturally, bisimides (I) g make you bobber Have solubility, also in plastics, the processing temperature of which is lower is already orange in color. The solubility of the bisimides (I) is increased the alkyl radical R influences 0 The longer R, the more soluble the bisimide (I) o For the Dye with R = methyl, the solubility in polystyrene is so reduced that Only at processing temperatures of 280 to 2900C are orange colorations acquired0 the The following examples are intended to explain the invention further.

The parts and percentages relate to the weight.

EXAMPLE 1 120 parts of perylenetetracarboxylic acid anhydride are used in 360 parts of water and 55 parts of 2-methoxyethylamine verrtibrt and heated to 130 to 135 ° C under pressure. The mixture is stirred for about 10 hours at this temperature until a sample has no free perylenetetracarboxylic acid mebr indicates After cooling down and releasing the pressure, the reaction mixture is diluted with water, filtered and washed with one percent aqueous warm sodium carbonate solution until the bark runs out, washed neutral and dried. 153 parts of perylenetetracarboxylic acid bis (ß-methoxyethylimide) are obtained in the form of a red dye powder Analysis: 030H2206N2 (507) berO 71.1 C 4.4 H 19.0% 0 5.5% N gefO 71.5% C 4.5 ffi H 19.1% 0 5.6% N Example 2 In 800 parts Ethylene glycol is 110 parts of perylenetetracarboxylic anhydride and 56 parts of 2-methoxyethylamine heated with stirring to 170 to 17500 and kept at this temperature for so long, until no more perylenetetracarboxylic acid can be detected. This is after about 1 hour the case. It is allowed to cool to about 15,000, diluted with 200 parts of dimethylformamide, filtered at about 40 ° C, the filter material washes with 100 parts of dimethylformamide, then with water and dry.

125 l of perylenetetracarboxylic acid bis (ß-methoxyethyl oxide) are obtained as red powder.

Analysis: C30H22O6N2 (507) calc. 71.1% C 4.4% H 19.0% 0 5.5% N found. 69.7% C 4.8% H 19.9% O 5.8% N Example 3 If you proceed as in Example 1 described, but uses 64 parts instead of 55 leile 2-Methoxgäthylamin 2-Ethoxyethylamine and holds for 5 hours at 130 to 135 ° C, is obtained after working up 161 parts of perylenetetracarboxylic acid bis (ß-ethoxyethylimide) in the form of a red dye powder.

Example 4 In 400 parts of ethylene glycol there are 110 parts of perylenetetracarboxylic acid anhydride and 67 parts of 2-ethoxyethylamine heated under Rübren to 155-1600C and so long held at this temperature until no more perylenetetracarboxylic acid can be detected ist0 This is after about 1 hour of the balls. Allow to cool to 800C, dilute with 300 parts of methanol, filtered at about 40 ° C, washes the filter material with something Methanol, then with water and dry. 140 parts of perylenetetracarboxylic acid bis (ß-ethoxyethylimide) are obtained as red powder analysis: 032H2606N2 (535) calc. 71s9% C 4.9% H 5.2% N violin 71.4 r c 4.9% H 5.2% N Example 5 The procedure is as described in Example 2, however, instead of 56 parts of 2-methoxyethylamine, 72 parts of 2-n-propoxyethylamine were used. The reaction mixture is diluted with methanol (instead of dimethylformamide). After working up, 155 parts of perylenetetracarboxylic acid bis (ß-n-propoxy-ethylimide) are obtained as red powder.

Example 6 The procedure described in Example 5 is used but instead of 72 parts of 2-n-propoxyethylamine, 82 parts of 2-n-butoxyethylamine are obtained one 157 parts perylenetetracarboxylic acid-bis- (ßn -butoxy-ethylimide) as a red powder, example 7 full tone stove-enamelling (10 percent) a) full tone paste (30 percent) 3 parts of the dye of Example 1 are mixed with 7 parts of a varnish-like Binder (= Grinding Base 100 S from Lawter Chemicals Inc., Chicago) a three-roll mill with 6 passages at 80 atmospheres to a 30 percent full tone paste processed0 b) Full-tone lacquer paste (10 percent) 2 parts of full-tone paste a) are mixed with 4 parts of a binder mixture, consisting of 1 part of a soybean oil modified Alkydharzess 2 parts of an alkyd resin modified with synthetic fatty acid and 3 parts of a solvent-free melamine resin mixed0 c) Implementation the coloring With a film applicator the lacquer paste b) is applied in one layer of 100 ju applied to cardboard and baked for 45 minutes at 120 ° C. You get a very opaque bluish-tinged red color with excellent light and very good weather resistance 0 Used instead of the dye in the example 1 the dye of example 3, a very similar coloration is obtained, example 8 Stoving enamel (white waste 1 o 20) a) White paste (30 percent) 42 parts a binder (obtained by mixing 1 part of a soybean oil modified Alkyd resin and 2 parts of one modified with synthetic fatty acid Alkyd resin) with 30 parts of titanium dioxide (rutile goods), 22 parts of a solvent-free Melamine resin and 6 parts of a colloidal silicon dioxide on the three-roll mill Rubbed at 80 atm with 6 passages to a 30 percent white paste.

b) LackPaste 0.5 parts of the full tone paste (30 percent) from the example 7 a) and 10 parts of white paste (30 percent) a) are applied to a leller rubbing device mixed and rubbed, c) Carrying out the staining with a film puller Apply the varnish paste b) with a layer thickness of 100 / u on cardboard and 45 Baked in the drying cabinet at 12,000 minutes.

There are bluish red colorations with excellent light and very good weather resistance.

If the dye of Example 1 is used instead of the dye of Example 3, a very similar coloration is obtained.

Example 9 Stoving enamelling (white waste 1:20; from dye paste) a) 69 leile of a concentrated by redissolving the dye of Example 2 Sulfuric acid obtained finely divided aqueous 29 percent dyestuff paste with 64 leile of a solvent-free alkyd resin modified with soybean oil and 16 parts bis-ethyl hesylpbtbalat on an ireiwalzenstubl with 6 passages at 60 atü processed into a full-tone paste by flushing.

b) 66 parts binder, obtained by mixing 70 parts solvent-free alkyd resin modified with soybean oil, 17.5 parts of bis-ethyl-hesyl phthalate and 12.5 parts Share a solvent-free melamine resin, come with 30 parts litandioxid (rutile goods) and 4 parts of a colloidal silicon dioxide on the Dretwalzenstubl rubbed into a titanium dioxide paste at 60 atmospheres with 6 passages.

c) 0.4 parts of the full tone paste prepared according to a) and 5 parts of the according to b) prepared titanium dioxide paste are mixed on a plate grater and rubbed. With this Zarbpaste, as in Example 7 c), a varnish spread is made which is baked for 45 minutes at 1200C. A strong color is obtained bluish red coloring with very good lightfastness.

The dye of the example is used instead of a dough 2 71.5 parts of a correspondingly prepared 28 percent dough of the example 4, a very similar coloration is obtained. Example 10 Soft PVC (Og 1 percent transparent dye): 0.05 parts of dye, obtained according to Example 1, are mixed with 50 parts of a mixture of 65 parts of polyvinyl chloride powder and 35 parts of diethylhexyl phthalate and 2 parts of dibutyl-tin-bisthioglycolic acid hexyl ester on a rolling mill 150 to 1600C homogenized (duration: approx. 8 minutes), rolled into skins and on a Calender mill smoothed. Blue-red colored pelts are obtained with excellent Fastness to light and plasticizer 0 Example 11 Weicb-PVC (White Veracbuitt 1:10) 0.25 Parts of dye, obtained according to Example 1, are mixed with 2.5 parts of litandioside (rutile goods) and 50 parts of a mixture of 65 parts of polyvinyl chloride powder, 36 parts of di-ethylhexyl phthalate and 2 parts of dibutyl tin bis-thioglycolic acid hexyl ester on a mixing roll mill Homogenized at 150 to 160 ° C (Duration: approx. 8 minutes), on skins rolled and smoothed on a calender mill. Blue-red colored pelts are obtained with excellent light and plasticizer fastness.

Example 12 Soft PVC (full tone) Proceed as in Example 11, but uses 0.5 part instead of 0.25 parts of dye and titanium dioxide instead of 2.5 parts 0.25 parts, the result is brightly blue-red colored pelts with excellent light- and plasticizer fastness.

Example 13 Hard PVO (0.1 percent transparent color) 0.1 part Dyestuff obtained according to Example 1 are made with 100 parts of polyvinyl chloride powder (Suspension or emulsion goods) and 2 parts of dibutyl tin bis-thioglycolic acid hexyl ester Homogenized on a mixing roll mill at 150 to 160 ° C (duration: about 8 minutes) The The rolled sheet obtained are loaded on a plate press at 1400C with approx. 0.4 kg / cm2 pressed into sheets0 This gives blue-red pressed articles with excellent lightfastness.

If instead of the dye of Example 1, the dyes are used of Examples 3, 5 or 6, very similar colorations are obtained.

Example 14 Hard PVO (full tone) 1 l part dye, obtained according to the example 1, is made with 100 parts of polyvinyl chloride powder (suspension or emulsion goods), 0.5 parts of litandiosld (rutile ware) and 2 parts of dibutyl-tin-bis-tbioglycolic acid besyl ester Homogeneous @ ized on a mixing mill at 150 to 1600C (duration: approx. 8 minutes). The rolled sheets obtained are placed on a plate press at 1400C with Approx.0 0.4 kg / cm2 pressed into plates0 This gives compacts which are brightly blue-red in color with excellent lightfastness.

If the dyes of Examples 3, 5 or 6 are used, one obtains very similar colorations.

Example 15 Polyethylene (0.05 percent transparent coloring) 0.05 leile dye, obtained according to Example 1, are in a drum mixer at 100 Share dry mixed polyethylene powder (high-pressure goods). The mixture is on melted in a screw press at a cylinder temperature of 160 to 20,000 and homogenized0 The colored plastic mass is hot-knocked on the nozzle head or granulated by pulling threads with cooling0 The granules obtained in this way is then injected into moldings in an injection molding machine at 200 ° C or pressed to arbitrary bodies on presses. A yellowish bluish-red color is obtained Compacts with excellent lightfastness 0 Example 16 Polyethylene (white waste 1:10) 0.1 part of the dye of Example 1 is mixed with 100 parts of polyethylene powder (High-pressure goods) and 1 part of titanium dioxide (rutile goods) as indicated in Example 15 mixed and processed into molded bodies0 This gives blue-red compacts with very good lightfastness Example 17 polystyrene (0? o5 percent transparent coloring) 0.05 part of dye, obtained according to Example 4, is used in a drum mixer 100 parts of ground polystyrene block polymer dry mixed. The mixture is done on a screw press at a cylinder temperature of 200 to 2500C melted and homogenized. The colored plastic mass is produced by hot knocking on the nozzle head or granulated by drawing threads with cooling. The granules inherited in this way is then molded in an injection molding machine at 200 to 250 ° C sprayed or pressed to any body on presses. You get luminous orange injection molded parts with excellent lightfastness that fluoresce in a similar shade.

Instead of a polystyrene block polymer, a polystyrene emulsion polymer can also be used or suspension polymer or

Copolymer used with butadiene and acrylonitrile or acrylic esters werden0 If instead of the dye of Example 4, the dyes of Examples 3, 5 or 6, very similar colorations are obtained. Example 18 Polystyrene (White cut 1:10) 0.1 part of the dye of Example 4 is mixed with 100 parts ground polystyrene block polymer and 1 part of titanium dioside, as in Example 17 indicated, mixed. The mixture is melted, homogenized and granulated. The granulate obtained in this way is injected or pressed to form moldings (processing temperature 200 to 2500C). Bright orange-colored injection molded or pressed parts are obtained with very good lightfastness. Instead of the dyes of Example 4, the Dyestuffs of Examples 3, 5 or 6, 8o give very similar colorations.

Example 19 The procedure described in Example 4 is used but instead of 110 parts of perylenetetracarboxylic acid anhydride, 119 parts of monochloroperylenetetracarboxylic acid anhydride, that's how you get one very similar dye.

The monochloroperylenetetracarboxylic acid or ibr anhydride is based on the following How to prepare: 100 parts of perylenetetracarboxylic anhydride are in 700 parts Nitrobenzene with 12 parts of iodine and 390 parts of sulfuryl chloride heated to 65 to 700C and stirred for two hours at this temperature. The mixture is heated further to 80 to 850C and stays at this temperature for 7 hours. After cooling to room temperature filtered, the filter cake washed with nitrobenzene, methanol and water and dried. A chloroperylenetetracarboxylic anhydride with a is obtained in very good yield Carbon content of 8.9%, corresponding to the monochloroperylenetetracarboxylic acid anhydride.

Claims (4)

Patent claims 1. Dyes of the Perglen-3,4,9,10-tetracarboxylic acid diimide series of the formula in which R is alkyl having 1 to 8 carbon atoms, X is chlorine or bromine and n is a Zabl between 0 and 3 and the radicals R can be the same or different. 2o dyes according to claim 1, characterized in that n = O is 0 3. VeXabren for the production of dyes according to claim 1, by condensation of perylene-3,4,9,10-tetracarboxylic acid or its dianbydride with primary aliphatic Amines in heat, characterized in that the primary amines are ether amines of the formula H2N-CH2-CH2-OR or mixtures of these amines are used, where R is the one in claim 1 mentioned meaning bat. 4. Use of the dyestuffs according to Claim 1 for coloring paints, Resins, printing inks, glue paints and plastics in bulk.